Process for the production of isoindolenine derivatives



Unimd SW68 Pat n Claims priority, application Great Britain August 25, 1949 11 Claims. (Cl. 260-250) This application is a continuation-in-part of our c0- pending application Serial No. 180,696, filed August 21, 1950, entitled New Intermediate Products.

The present invention relates to new intermediate products and to processes for their production, in particular it relates tonew phthalocyanine intermediates.

It is an object of the invention to provide new intermediate products which may be used for the production of phthalocyanines.

A further object of the invention is to provide new intermediate products which may be used for the production of phthalocyanines under gentle conditions, especially at lower temperatures.

9 A further object of the invention is to provide very reactive new intermediate products which may be utilized in the organic synthesis.

A still further object of the invention is to provide new methods for the production of said new intermediate products.

Another object of the invention is to provide processes for the production of said intermediates on atechnical scale.

2 Haddock expressly declares, however, that this intermediate or any other intermediates of the phthalocyanine synthesis except theafore-mentioned mono-imino-phthalimide could neither be isolated nor determined.

A. It has now been found that such hitherto unknown intermediate products of the phthalocyanine synthesis are obtained by heating o-arylene dicarboxylic acids, their nuclear substitution products or functional derivatives thereof in the presence of substances giving oif ammonia under the reaction conditions, for instance urea, as well as "in the presence of preferably at least equimolar Additional objects and features of this invention will become apparent as the following description proceds.

According to the prior art processes phthalocyanines have obtainable according to British specification No. 520,415,

for instance, by heating phthalimide with urea and ammonium molybdate.

According to theoretical considerations Haddock (Journal of the Society of Dyers and Colourists 61 (1945), page 71) thinks it possible that inthe phthalocyanine synthesis an intermediate could be formed which contains 3 nitrogen atoms in one aromatic radical in a combined state and formulated this hypothetical intermediate as follows:

C/ in amounts of anions which are stable under the reaction temperatures, whereby preferably nitrate ions are used and in case functional derivatives of o-arylene dicarboxylic acids containing carbonyl groups or these acids are used as reactants, in the presence of catalysts promoting formation of phthalocyanine from o-arylene dicarboxylic acids and, if desired, in the presence of inert solvents, to temperatures of about 200 C.

The intermediate products obtained according to the present invention are believed to be derivatives of isoindolenine.

wherein X stands for hydrogen or for zero to four organic or inorganic radicals, for instance for alkyl radicals such as CH3, CzHs, C4H9, C5H11 etc., alkoxy radicals such as CH3O-, C2H50 etc., aroxy, alkyl mercapto and aryl,

mercapto radicals, heterocyclic radicals, further for halogen, -NH acyl, .NO2, COOH, SO3H, -SOzNHz, 'SO2NH alkyl, SOzN(alkyl)2 groups etc. X may also stand for one or two cyclic groups condensed to the bon zene nucleus of the isoindolenine. One or more of the carbon atoms of the carbocyclic nucleus or carbocyclic nuclei may be replaced by hetero atoms; for instancefby one or two N- or S- atoms. R1, Rz and R may stand forhydrogen or also for organic or inorganic radicals, for instance for alkyl radicals such as CH3, C2H5, C4Hs, C8H17, C14H29 etc. These alkyl radicals may be substituted, for instanceby hydroxy groups etc., for cycloalkyl-, aralkyland for aryl radicals such as phenyl, substituted phenyl radicals, naphthalene or anthraquinone radicals, for other polycyclic radicals, for heterocyclic radicals and for acyl radicals, such as formyl, acetyl, benzoyl etc. Furthermore, R2 or Rs may stand for S0z aryl groups. R2+R3 may also stand for an alkylene radical which may contain hetero atomspin its chain, for example the divalent radicals --(CH2)5-- and both free valences being attached to-the nitrogen atom). The radicals R1 and R2 (R3 respectively) may form a cycloalkylene ring, for instance R1+Rz may be and o-dinitriles.

As starting materials for the process according to the present invention besides phthalic acid and the functional 3 derivatives thereof any of their nuclear substitution products containing the above mentioned radical X may be used. As polynuclcar and heterocyclic o-dicarboxylic acids may be mentioned naphthalene-o-dicarboxylic acids, anthracene-o-dicarboxylic acids, pyridine-o-dicarboxylic acids, quinoline-o-dicarboxylic acids etc.

Of course, instead of the aforementioned dicarboxylic acids their functional derivatives may be used, such as, for instance, anhydrides, ammonium salts, imides, monoimino-imides, monoand diamides including ureides, o-cyanocarboxylic acids, whereby the carboxylic acid group may be present in form of said functional derivatives,

It is to be understood that the o-dicarboxylic acids, their nuclear substitution products or the functional derivatives thereof which are known as starting materials in the production of phthalocyanines according to the prior art processes may also be used as starting materials for the production of the amino-imino-isoindolenines according to the present invention.

When using dicarboxylic acids or their functional derivatives containing carbonyl groups as starting materials it is necessary to add a catalyst for carrying out the reaction. The same catalysts may find application which may be used in the production of metal phthalocyanines by the conventional methods, for instance, from phthalic anhydride, according to the so-called urea process. Especially suitable catalysts are molybdic acid or its salts, for instance, ammonium molybdate. On starting from o-arylene dinitrile the addition of a catalyst may be dispensed with.

The term substances giving off ammonia means the compounds which may be employed on carrying out the phthalocyanine synthesis according to the urea process. Such products are, for instance, urea, guanyl urea or biuret which are used in excess.

For accomplishing the reaction according to the present invention it is further necessary to add such anions to the reaction mixture as are stable under the reaction conditions applied. These are in the first line anions of inorganic acids, such as, for instance, of nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, however, good results can also be attained by means of anions of organic acids, such as, for instance, of aliphatic and aromatic sulfonic acids as well as of methane sulfonic acid, methionic acid, toluene sulfonic acid, and of naphthalenemonoand polysnlfonic acids, for instance, naphthalene-1.S-disulfonic acid. These anions are to be used in at least equimolar quantities referred to the dicarboxylic acids or their functional derivatives. If minor quantities are employed the yield is generally reduced. Of course, larger quantities than the equimolar ones may also be used without the yield being impaired thereby.

When using o-arylene dicarboxylic acids or their functional derivatives containing carbonyl groups as reactants it is of advantage to use nitrate ions which yield with the corresponding l-amino-3-imino-isoindolenines insoluble, salt-like compounds which are less afiected by changes of temperature. However, on using o-dinitriles as starting material other anions yield equally good results. The said anions are advantageously charged in form of their ammonium salts or also as free acids which may be linked to the urea whereby it .is of no consequence whether the anions are added to the reaction mixture already before or after the beginning of the reaction. In the production of the new intermediate products according to the present invention it is immaterial whether the components are simply melted or Whether a solvent is added. In the first case, the substance giving otf ammonia which is preferably used in excess acts as diluent. In the second case, as solvents preferably higher boiling hydrocarbons or their substitution products, such as, for instance, solvent naphtha, nitrobenzene, dior trichloro-benzene, chloro naphthalene are suitable, but also pyridine or quinoline may be used.

The reaction is generally initiated at temperatures of or above about C., i. e. temperatures whereat the starting material generally begins to melt. The reaction temperature may be raised to the temperature usually applied in the production of phthalocyanine according to the above described process whereby reaction is completed within a short period of time without phthalocyanines being formed thereby. Otherwise, the same conditions are applied which are customary in the production of phthalocyanines according to the above-said urea process.

Methods to be applied for isolation of the aminoiminoisoindolenines or their salts obtained according to this process differ somewhat depending upon whether the reaction has been performed with or without cliluents. On working without dilnents the melt is taken up with organic solvents, for instance, acetone, alcohols, water'or in mixtures thereof, and is further diluted with water. The salts of the amino-imino-isoindolenines already precipitate if anions yielding diificultly soluble salts, such as nitrateor aryl sulfonic acid anions were used for accomplishing the reaction. If, however, such anions were used as give easily soluble salts of the amino-iminodsoindolenines, the amino-imino-isoindolenines are preferably precipitated by addition of nitrate ions in form of their salts or by addition of concentrated aqueous salt solutions, such as ammonium chloride-, sodium chloride, or ammonium phosphate solutions.

When the reaction has been accomplished .in the presence of solvents isolation may be efiected by simply separating the amino-imino-isoindolenines from the solvents wherein the amino-imino-isoindolenines in form of their salts are insoluble. They may further be purified by means of solvents.

This process is described and claimed in our copending application Serial No. 180,696 of even date, entitled New Intermediate Products.

B. The new intermediate products may also be obtained by adding ammonia or its derivatives to o-arylene dinitriles or the functional derivatives of o-arylenedicarboxylic acids being free from carbonyl groups which may contain hetero atoms in the aromatic ring or to the nuclear substitution products thereof, if desired, in the presencev of solvents and/or catalysts and/or under pressure.

Suitable starting materials for this reaction are besides phthalonitrile any of its nuclear substitution products containing the radical X-indicated in the above formula-may be used. As polycyclic and heterocyclic o-dinitriles may be named: naphthalene-o-dinitriles, o-dicyano pyridines, 2.3-dicyan0 pyrazine etc. Compounds containing four cyano groups are also suitable such as l.2.4.S-tetra-cyano-benzene and 3.4.3.4'-tetracyano-diphenyl. It is to be understood that all dinitriles or functional derivatives of o-dicarboxylic acids being free from carbonyl groups which are known as starting materials in the production of phthalocyanines may also be used for producing the new intermediates according to the present invention.

According to this process suitable derivatives of ammonia are for instance: primary and secondary amines such as methyl amine, dimethyl amine, ethyl amine, butyl amine, dodecyl amine, cyclohexyl amine, benzyl amine, aniline, amino diphenyl, naphthyl amines, amino anthraquinones etc., substituted amines such as alkanolamines, substituted anilines and substituted naphthyl amines. Furthermore, sulfonamides such as p-toluene sulfonamide, heterocyclic nitrogen compounds such as piperidine and morpholine, and N ,N -substituted hydrazines such as N-amino-piperidine, N ,N -diphenyl hydrazine may be used in the above mentioned reaction. Generally, the derivatives of ammonia are suited which are stable under the reaction conditions. The addition of ammonia or of a said derivatives thereof to the aforementioned functional derivatives of o-arylene dicarboxylic acids being free from carbonyl groups, i. e. principally to the o-dinitriles, can be effected in various manners. The temperatures applied in this reaction rarely exceed to 160 or 170 C. Thus, for instance, the said reactants maybe treated with ammonia or its derivatives without any additions and in the absence of solvents at temperatures above 100 0., preferably in the autoclave, under a pressure of up to about 120 to about 150 kg./cm. After completion of the reaction the excess of ammonia or derivatives thereof respectively is removed. The reaction product thus obtained is amino-imino-isoindolcnine in technically pure form which may directly be used or previously further purified by treating with water or organic solvents. In order to facilitate purification it maybe of advantage to carry out the reaction in the presence of inert organic solvents, for instance, of a low alcohol. Especially useful are alcohols containing'at least one -CH2OH group. On using a higher boiling solvent, for instance, polyvalent alcohols, it is not necessary to carry out the reaction in the autoclave, but it is sufficient to dissolve the starting materials in the autoclave and to pass ammonia or derivatives thereof in the gaseous stateover or through the solution heated to temperatures from about 100 to about 160 C. If the ammonia derivative to be added has a sufficiently high boiling point, for instance, monoethanolamine, it is sufficient to dissolve the starting material in this ammonia derivative and to heat, for instance, to temperatures between 70 and 140C. In this way, the reaction proceeds practically quantitatively without further additions being required.

The reaction may also be performed in the presence of anions which are stable under the reaction temperatures applied. The anions may be charged, for instance, in form of their ammonium or urea salts, such as ammonium nitrate, ammonium chloride, ammonium phosphate and urea nitrate. In this case it is possible to carry out the reaction in the presence of urea or ammonia. When processing in this manner the corresponding salt of the 1-amino-3-imino-isoindolenine is produced which may be purified as described in the foregoing.

If a catalyst is added, the reaction may also be accomplished at lower temperatures. Suitable catalysts are heavy metal compounds, especially those which may be used for the production of phthalocyanines. Asexamples may be mentioned copper salts, especially salts of bivalent copper andsalts of cobalt, nickel, iron, cadmium, zinc,

or also activated metals, for instance, Raney-nickel. Also in this case, it is of advantage to carry out the reaction in the presence of a solvent and, especially, in the presence of monoor polyvalent alcohols, especially primary alcohols. The said catalysts are added to the solution of the starting material in quantities of about 01-50% calculated on the starting material used and the solution is saturated with ammonia or its gaseous derivatives mentioned above or a stream thereof is passed over the solution. When using liquid or solid derivatives of ammonia these may be introduced into thesolution. In this case, the addition of special" solvents may be dispensed with as, for instance, in the case of monoethanolamine. The reaction mostly proceeds already at room temperature. The reaction results in the formation of the free base which mostly crystallizes from the solvent and may be separated in known manner. However, the base may also be isolated in form of its salts, for instance, by addition of nitrate ions, or in form of its carbonate by introducing carbon dioxide.

Besides the said heavy metal compounds also metal alcoholates or substances or mixtures acting like alcoholates or also alkali metal amides promote the addition of ammonia or the said derivatives thereof to the said functional derivatives of the o-arylene dicarboxylic acids being free from carbonyl groups. However, on using about 40 to 65 C. However, it may be sometimes of.

these'products care has to be..take1i that the reaction temperatures are kept so low as to prevent the formation of phthalocyanine at all or, at least, to a material extent,

i. e. temperatures up to about C. are to be applied.

Suitable metal alcoholates are those of alkali metals, alka- I line-earth metals and aluminum whereby the alcohol also be performed under conditions effecting the formation of alcoholates during reaction, for instance, when using alcohols together with the said metals or when using alkali metal amides together with an alcohol. However, the same effect is also attained by charging the said metal amides together with liquid ammonia or acid amides, such as formamide, acetamide. Mixtures of alkali metal or earth alkali metal alcoholates and formamide may also be used. The amount of alcoholates or amides respectively required for accomplishing the reaction may vary in a wide range. Thus, for instance, it is possible to obtain good yields with l per cent or less of alcoholate calculated'on the functional derivative of the o-arylene dicarboxylic acid being free from carbonyl groups. Similar yields are attained on using quantities corresponding to 1 mol of alcoholate per 1 mol of the aforementioned derivative or quantities exceeding said proportion.

Suitable solvents are in the first line .the lower monoor polyvalent alcohols, such as, for instance, methyl-, ethyl-, propyl-, butyl-, or amyl-alcohol or glycol or, as already mentioned above, acid amides or liquid ammonia. The said solvents may also be used together with indiflferent solvents miscible therewith. As examples may be mentioned aromatic hydrocarbons such as benzene and toluene, furthermore tetrahydrofuran or diethyl glycol.

On using the last-mentioned catalysts the optimum reaction temperatures vary in a wide range and depend on the character of the metal-alcoholate or -amide and of the solvents or solvent mixtures used. On processing with liquid ammonia the boiling temperature of ammonia is generally sufficient to accomplish the reaction whereas in other cases the optimum reaction temperature is at advantage to process at temperatures up to or above 100 C. Care has to be taken that the upper limit of the reaction temperature is not exceeded since in this case the formation of phthalocyanine takes place. "In spite of this fact, it is possible in some cases to operate Within this critical temperature range if the reaction is performed within a very short time so that only .1-amino-3- imino-isoindolenines are principally formed, i. e. if reaction is stopped before formation of phthalocyanine starts or directly after starting of the dyestuff formation.

On using the said catalysts it is also possible to charge, besides the said arylene o-dinitriles, the correponding hydrogenated dinitriles, for instance A-4.5-4-methyl-tetrahydro-phthalonitrile. The corresponding hydrogenated 1- amino-S-imino-isoindolenines are thus obtained.

This process is described and claimed in our copending application Serial No. 307,903 of even date, entitled Process for the Production of Isoindolenine Derivatives.

C. When using the last-mentioned catalysts the process may be carried out by reacting o-arylene dinitriles with the alcoholates in the absence of ammonia or amines to form the corresponding l-alkoxy derivatives of the 3- imino-isoindolenine which are described in the co-pending application Serial No. 180,695 of even date relating to Process of Dyeing and Printing and reacting the l-alkoxy-3-i.mino-isoindolenines thus obtained which may be monomeric as well as condensed ones depending on the reaction conditions applied, after isolation or also in the reaction mixture with ammonia or the aforesaid deriva-. tives of ammonia (see part B). The monomeric or condensed alkoxy derivatives may carry nuclear substituents which are described in the above formula (see part A) It is not absolutely necessary tov under X. They may also contain hetero atoms in the carbocyclic ring and" aromatic ringscondensed to the benzene nucleus. If'ammoniaor its gaseous derivatives are used. for this reaction, the same are preferably passed through the solutionof theaikoxy compounds in an inert organic'solvent, such. as, for instance, benzene, acetone or in alcohol; or the ammonia or the derivatives thereof are dissolved in alcohol and added to the solution ofthe alkoxy' compounds. However, salts of ammonia or derivatives thereof may also be used'which are reacted with the alkoxy. compounds in form of their solutions. For accelerating the reaction. it may be sometimes of advantage to process in thepresence of some water in the reaction solution.

Ifmonomeric alkoxy compounds" are used'for carrying out the reaction the monomeric amino-imino-isoindolenines are obtained. If, however, condensed alkoxy-iminoisoindol'eni'nes are employed. as reactants, condensed amino imino-isoindolenines may be obtained, if the reaction is accomplished within a short time. Condensed amino-imino-isoindol'enines. comprisev compounds wherein one carbon atom each belonging to the heterocyclic nucleus-of two molecules of the isoindolenine are connected by a nitrogen bridge and which may contain alcohol as an addition. T hey correspond to the formula wherein, X is. defined as in the above formula of part A, R being CH3, Cal-I5, CZSHL, CHS or CsHn and other alkyl radicals and nbeing an integer from 1 to 6.

If the ammonia or the amines are reacted for a prolonged time and/or at higher temperatures, for instance up. to about 160 C., the nitrogen bridge is split off and a further molecule of ammonia is added so that, for instance, in the case of the dimeric product two molecules of monomeric amino-imino-isoindolenine are formed.

When using primary amines as derivative for carrying out the above reaction, also the imino group of alkoxyimino-isoindolenine may be replaced by these primary amines.

Isolation of the amino-imino-isoindolenines thus obtained from the reaction solutions as far as they are crystallized may be accomplished in known manner by simply separating out. The non-crystallized portions may be isolated either after concentrating the solution, preferably in vacuo, or by adding the aforesaid anions forming ditficultly soluble salts.

Besides the said alkoxy-imino-isoindolenines also the corresponding thio-compounds may be used for carrying out the reaction with ammonia or its above mentioned derivatives. Thus, for instance, according to Porter, Robinson and Wyler (Journal of the Chemical Society, London, l94l, page 620) a mercapto compound is obtained which is indicated as o-cyano-thiobenzamide by addition of sodium sulfhydrate to phthalonitrile. The same compound may also be produced by reaction of anhydrous sodium sulfide upon phthalonitrile in methanol. The products prepared according to these two processes are believed to be 1-mercapto-3-imino-isoind.olenines. The corresponding amino-imino-isoindolenines are ob tained by reacting the said mercapto compounds or the alkyl ethers thereof with ammonium nitrate in the presence of a solvent or suspending agent and isolating the nitrates of the amino-imino-isoindolenine thus formed.

Instead of using the said alkoxy-imino-isoindolenines it is also possible to charge alcohol-hydrochloric-additionproducts obtained from aromatic o-dinitriles according to Pinner (Die lmido'zither und ihre Derivate, Berlin 1892, page 2 etc.) which are almost identical with the above-mentioned alkoxy-imino-isoindolenines except that they contain hydrogen chloride in the molecule, Hence it follows that in. the reaction of" the products obtained according to Pinner with ammonia or its derivatives which is preferably carried out in alcohol, care has to be ta ken that processing is done at very low temperatures,

for instance, at 0C. in order to avoidsaponification by the hydrochloric acid present.

This process is described and claimed in our copending application Serial No. 307,905 of even date, entitled Process for the Production of isoindolenine Derivatives.

D. In the production of the N-substituted derivatives tioned derivatives of ammonia, for instance primary orsecondary aliphatic, aromatic, cycloaliphatic, polycyclic and heterocyclic amines, which may be substituted such as allianolamines, the derivatives'of aniline or naphthylamines etc., N N -substituted hydrazines, furthermore piperidine, morpholine and hydroxylarnine. This exchange reaction generallyproceeds smoothly with splitting ofii ammonia. The reaction is'most easily performed with primary amines whereby the reaction velocity is often satisfactory at room temperature. tocarry out the reaction in an inert organic solvent. Suitable solvents are in the first line alcohols, especially methanol orv also water or forrnamide. When the reaction is accomplished by means of liquid amines, such as, for instance, ethanol amine, anisidine. an excess of these products may act as solvent. In the case of'primary amines either the amino group alone or also the amino group and the imino group may be substituted. The weakly basic aromatic amines, for instance, aniline substi tute, the amino group only when the reaction is performed under gentle conditions. The imino group is substituted athigher temperatures and when the reaction the reaction is accomplished at temperatures up to about 160 and. 170? C.

On using strong basic, primary, aliphatic amines the exchange of the, imino group is so easily effected that generally derivatives substituted at both nitrogen atoms can be isolated. On using secondary amines derivatives are obtainedwhich are substituted at one nitrogen only. It is often possible to exchange the substituted amino or imino group vice versa by treatment with ammonia in excess. against a non-substituted amino or imino group. It is. further possible to replace a substituted aminoor imino. group by amino groups substituted by a different radical. Also N-substitutionproducts which contain dif ferent substituents on the amino and imino group may be obtained. By using aliphatic diamines such as polymethylene diamines products may be obtained in which both N-atoms of the amino and imino group are linked, by a methylene bridge.

Isolation of the l-amino-3-imino-isoindolenines thus obtained may be accomplished in usual manner, for instance, by simply separating the portions crystalli zing out of the reaction solution. In other cases they. maybe precipitated and separated by adding solvents reducing their solubility and being miscible with the originally used solvent, for instance, hydrocarbons or ice water. However, anions may be added which yield difiicultly soluble salts, for instance, nitrate ions. Finally, the l-amino-B- imino isoindolenines may also be obtained by distilling off the solvent used in the reaction.

The, amino-iminorisoindolenines obtained according to the above described processes represent new products. They are generally colorless. to yellow colored and most readily crystallize. They are stable and fast to storing in It is often ofadvantage their crystalline form. Their melting points are generally above 100 C. On melting, in most cases, splitting oil of ammoma or the derivatives thereof and decomposition take place, colored melts being left thereby.

The amino-imino-isoindolenines partlydissolve in waindolenines wherein nitrogen is substituted often behave,

differently as, to their solubility from the unsubstituted ones. The salts when heated are also soluble in a number of organic solvents, such as in substituted aromatic hydrocarbons, such as nitrobenzene, chlorobenzene and acid amides, furthermore in tertiary bases, for instance, pyridine. Also in this case, decomposition, i. e. splitting off of ammonia or derivatives thereof mostly takes place. The salts are generally dilficultly soluble in aliphatic and aromatic hydrocarbons as well as in ketones, ethers etc. With dilute alkali lyes the hydrates or the free base respectively form alkali metal salts being easily soluble in water.

The l-amino-3-imino-isoindolenines are gradually saponified in aqueous solutions, the corresponding monoimino arylene dicarboxylic acid amides being formed thereby. Decomposition is promoted by heating or adding dilute'acids or alkali lyes.

I'Ihe salts of 1-amino-3-imino-isoindolenines generally containone acid residue per one mol of isoindolenin'e however, salts have been isolated containing less, for instance, /2 or /3 equivalent of the acid per 1 mol of isoindoleninewhich is mostly present in a combined state, for instance, in the case of nitrate. The salts may also be recrystallized from aqueous ammonia solutions under;

certain conditions. On the other hand, in any case, the free base or its hydrate respectively is obtained by adding equivalent amounts of alkali lye to the salts.

The 1-amino-3-imino-isoindolenines, as far as their amino group is not substituted, are accessible to many reactions of 'the primary amines. For instance, they maybe acylated or alkylated. With diazonium compounds they yield diazo-amino compounds. They can easily be reacted with aldehydes.

to form higher molecular products mostly containingalkoxy groups in the molecule. The l-amino-3-imino-isoin- Aromatic o-dinitriles may be added in the presence of alkali metal alcoholates dolem'nes are converted with phenyl hydrazine into in-f tensely colored compounds. On heating the Lamina-3 imino-isoindoleniues in high boiling solvents for a longer time ammonia or, if N-substituted compounds have been used, the derivatives thereof are split oil and condensation products are obtained which contain i. a. tricyano cyaphenine. On heating the 1-amino-3-imino isoindolenines in pyridine-water-mixtures in the presence of so dium hydrosulfite generally blue colored solutions are obtained which by the action of excess sodium hydrosulfite or atmospheric oxygen easily decolorize again.

On heating solutions of aminoimino-isoindolenines with reducing agents, for instance, with formaldehyde or if reducing agents are used as a solvent, for instance,

formamide, more or less large quantities of metal-free phthalocyanines are obtained. On heating them together with metal salts and reducing agents the ,correspondin metal phthalocyanines are formed. t

The monomeric as well as the condensed aromatic 1-amiuo-3-imino-isoindolenines may be reacted with heavy metals forming complexes, if necessary, in the presence of solvents to form crystallizable complexes.

The l -amino-3-imino-isoindolenines according to the I present invention may be substituted as already mentioned above .in the carbocyclic ring by one or more radicals.

The compounds may also carry condensed aromatic or heterocyclic nuclei.

Besides the nuclear substituents the compounds may 'carry at the nitrogen of the imino and amino group the examples without being restricted thereto, the parts being by weight.

Example 1 32 parts of phthalonitrile are heated with 95.6 parts of liquid ammonia in a stirring autoclave of chromenickel-steel for 5 hours at 110-1l8 C. (about atmospheres overpressure). After cooling the NHs is blown oil and the solid, light blue-grey residue (37.6

parts) is ground several times with water previously heated to 40-50 C. and sucked off until the residue has no longer a bitter taste. For removing any slight amounts of phthalonitrile the residue is boiled OE With water, aboutLS parts of deep blue small needles of practically metal-free phthalocyanine remaining behind thereby. The aqueous extract solidifies on cooling to a viscous paste of colorless small needles of amino-imino-isoindolenine which after sucking oil, cautiously washing with some water and drying, melt at l 92195 C.

Example 2 128 parts of phthalonitrile are heated to 140 C. with 80 parts of ammonium nitrate in 4000 parts of liquid ammonia while stirring for 20 hours in an autoclave.

The crude amino-imino-isoindolenine-nitrate remaining after distilling, off the ammonia is purified by treatment with cold water and hot benzene.

Example 3 30 parts of phthalonitrile are dissolved at about C. in 32 parts of monoethanolamine and kept at this, temperature. After solidifying the reaction mixture is ground and washed with ethanol. l-Oxethylamino-3- oxethylimino-isoindolenine is obtained in quantitative yield. In order to prevent overheating and to facilitate isolation the reaction mixture may be diluted with a solvent, for instance, an alcohol.

Example 4 128 parts of phthalonitrile are mixed with stirring with I 250 parts of glycol and the mixture is saturated with ammonia at 50 C. The dinitrile dissolves during about 24 hours whereas the glycolate of 1-amino-3-imino-isoindolenine (CaHvNH-CzH-rOz) crystallizes. The glycolate is isolated by suction filtration at 0 C., washed with benzene and acetone.

When using in the above reaction starting materials containing contaminations the mixture is heated to about 80 C. towards the end of the reaction whereby the reaction product dissolves and the contaminations can easily be separated oil by filtration.

The reaction may also be conducted at higher temperatures, say up to about C. In this case it is preferable to dissolve the dinitrile in glycol and to add ammonia at decreasing temperatures.

The reaction proceeds in the same manner below 50? C., however, the reaction times are prolonged in the absence of catalysts such asalkali and metallic ions.

' Example 5 16 parts of phthalonitrile are dissolved in 50 parts of 9 t. 30 nd w i rassina ammo a ov rv the mixturestirred for 2+3 hOurseachatIZO -BQ? C., 100-110 c., 80-90 c., 50-60 c; and fin ally at 0 C. with cooling.

The molecular compound of amino-in inodsoindolenine with glycol CsH'IN3.C2HsO2 crystallizes in abundant quantity in analytically pure form and may be easily isolated by sucking off and washing with acetone.

Example 6 13 Parts of phthalonitrile and 0.1 part of copper chloride are stir'red into 100 parts of monoethanolamine.

Phthalonitrilegoes into solution and l-oxethylarnino laoxethylimino-isoindolenine crystallizes. Theproduet can.

easily be isolated in aquantitative yield by sucking olland washing with alcohol.v

Example 7 50 parts of phthalonitrile and 0.5 part of copper sulfate-are-suspended in 250 parts of methanol and-thernixture-is saturated with ammonia. Phthalonitrile gradually dissolves at 70 C. A blue-gray,- finely crystalline copper complex salt of amino-imino-isoindolenine precipitates. Moreover, parts of the free base CsH'zNs precipitate in coarse crystals. The chief portion remaining dissolved can be precipitated nitrate by stirring the mixture into weaiily acidified Water containing nitrate. A

quantitative total yield is obtained.

The reaction proceeds more slowly in formamide, however, may equally be performed in other alcohols, such Similar or better results are attained as ethanol, glycol. on replacing CuSOi by other copper salts, such as CuCl, CuClz, 2H2O; CuNOs.3H2O, glycocoll copper, acetylacetone-copper, or also salts of copper, nickel, cobalt, cadmium etc., or active metals, for instance, Raney-nickel. Depending on the conditions applied the reaction is accomplished within 2-70 hours.

Example 8 A sodium methylate solution consisting of 3 parts of sodium and 128 parts of anhydrous methanol is poured onto 128 parts of phthalonitrile.

The mixture is vigorously stirred with cooling, however, towards the end of the reaction which is accomplished within a few minutes the temperature is allowed to raise up to 50 C. or also upto the boiling point of themixture. The color of the mixture changes thereby from yellow to orange and finally to deep dark red brown.

As soon as thephthalonitrile has completelydissolved the. temperature is reduced below 50 'C. and gaseous ammonia is passed over the solution with stirring. After some time l-amino-3-imino-isoindolenine begins to precipitate as thick crystal paste. The mixture is further stirred for some hours, diluted with 128 parts of acetone, further saturated with ammonia, the temperature is lowerecl to 0 C., the solution is sucked offifthe precipitate is washed with acetone until the washing has become Example 9 50 parts of sodium are dissolved in SZOparts of anhydrousethyl alcohol. The mixture which solidifies after cooling is dissolved in 1130 parts of formarnide. At 50 C., 204 parts of 3.4-dieyano diphenyl are introduced with stirring until after a few hours the dinitrile has dissolved. The reaction mixture soon solidifies to a crystal paste slight self-heating.

which is cooled and kept at room temperaturegfor several, hours. The precipitated product is separated bysuetionr the part remaining dissolved is .precipitated by. adding, The ,monohydrate of ;l-amino-3-imino-S(or 6-) Water. phenyl-isoindolenine is obtained in excellent purity and yield from both parts by recrystallization froma,mix-- ture of acetoneand water (about 1:1).

Example 10 40'parts of calcium are dissolved in 400 parts of anhydrous methanol. 1130 parts of formamide areadded at room temperature, whereupon, 128 parts. of phthalonitrile are introduced. The solution is stirred fora few, hours at. 7080 C. The initially yellow solution which changes, to yellow green is introduced whencoldinto, a.,mixture of ice, ammonium nitrate and nitric acid, Theprecipitate formed thereby is sucked off and washedwith water.

After drying the crude product is boiled out withacetone.

The nitrate of the, amino,-iminoisoindolenine thus obtained is not yet quite pure. .Purjficaw. tion may be achieved as indicatedin Example; 13, .of; eopending application Serial No. 180,696. Reactionmay. also take place without the use of alcohol .in ,such a.-mat1 ner that the calcium is dissolvedin formamide; at temm and sucked off again.

peratures of about 70 C. and the phthalonitrile is'intr0- duced with stirring after cooling.

When working in this manner the possibility of dyestutf formation being initiated is much greater.

Example 11 14 parts of lithium are dissolved in 400,parts ofan- I 1130 partsof formamide. are added at.

hydrous ethanol. roonl temperature and 128 parts of phthalonitrile, are

introducedwith stirring. The reaction mixture is heated forsome hours to 70 80 C. Further processing isdone asindicated in Example 10. The,nitrate of,aminoimino-isoindolenine is obtained in a.yield =of 80%.=of, theory. Similar conditions as indicated. in example '10..

with regard to calcium may be applied in a reaction .car-. ried out without alcohol.

Example 12 46 partsof sodium are dissolved in 800..yp arts ,of

anhydrous methanol and after cooling there are introduced, with' stirring.12 8 parts of phthalonitrile diss0lving. .with,. 7 Into the mixture, is stirred v,asolu tion of 342 parts of p-toluene. sulfonamide;.,in ,800 parts.

of anhydrous methanol and the mixture is hea ted,.for..4 hon at-about 90.? C. The l-p-toluene, sulfonamino-B- imino-isoindolenine is thusformed.

By stirring the reaction mixture into an ammonium salt solution cooled with, ice the reaction ,produet.pre cipitates, The precipitate ispurifiedby boilingput with, ethanpland ,with benzene. This sulfonarnide, compound. does not form a ,difiicultly soluble nitrate.

Example 13 128 parts of phthalonitrile are introduced into a mixture of 8690 parts of piperidine and a sodium methylate' solution consisting of 2 parts of sodium and parts-of methanol.

The phthalonitrile dissolves within a very short time. The heat beingv set free is discharged. to suchlan extent that the temperature raises only to about 50C.

The 1-piperidino-3-imino-isoindolenine precipitates in colorlessneedles already at the reaction temperature or after-cooling. Isolation is effected by diluting 'the'reaction'mixturewith -lo0 parts of acetone. The-mixture is sucked 011 when cold and the precipitate-iswashed The". product obtainedwith cold acetone and benzene; is analytieallyapure and shows a flash point of-i.':C."

0n rieplacing piperidine by; morpholine the- -reaction." yields ,l-morpholino-imin o isoindolenine..= The-.product decomposes at about C. with -blue -;co lorati,on;; It

forms with ammonium nitrate1-amino-34mino-isoindo lenine,nitrate.

Example 14 parts of sodium are dissolved in 800 parts of,

anhydrous ethanol. 430 parts of piperidine are added and 204 parts of 3.4-dicyano diphenyl are dissolvedin themixture with stirring and heating.

The solution from which impurities, if any, may be removed by filtration is heated for 2-3 hours at about 901 C. and then cooled. The reaction mixture from which on longer standing small amounts of the base formed precipitate is then stirred into a mixture of ice and 200 parts of nitric acid. The nitrate of the 5-(or 6-) phenyll-piperidino-S-imino-isoindolenine is thus obtained in 7 good yield. The precipitate is sucked off, washed with water and dried. The product may be recrystallized from an alcohol-benzene-mixture (about 1:1). The nitrate melts at about 215-220? C. with dark coloration.

Accordingto elementary analysis the compound exhibits the following composition:

Calculated tor Found cm iu aNt C=64.05% C=64.74% H= 4.20% H= 6.72% N=15.85% N=15.91% O=14.28% 0=13.63%

By replacing piperidine by morpholine, aniline, dimethyl- Calculated tor Found OnHmOaNt C=55. 22% C=54. 51% H= 6. 44% H= 6. 11% O=18. 20% O=18. 17% N=2L 20% N=21. 21%

Example 16 80 parts of pulverized sodium amide are introduced into 850 parts of formamide in portions at 0 C. while stirring and cooling-with a freezing mixture of ice and sodium chloride. 128 parts of phthalonitrile are added inportions to the clear solution and the temperature is raised to 60-70" C. A yellow solution is obtained from which colorless prismatic needles precipitate.

After 6-8 hours the solution is cooled, the amino-iminoisoindolenine obtained in good yield is sucked off, washed with some formamide and acetone and dried. By introducing the filtrate into a mixture of ice and nitric acid containing as much nitric acid as is required for neutralization and salt formation, a further quantity of aminoimino-isoindolenine is obtained as nitrate.

Example 17 80 parts of pulverized sodium amide are introduced inportions at 0 C. into 1130 parts of formamide while stirring and. cooling with a freezing mixture of ice and sodium chloride. 204 parts of 3.4-dicyano diphenyl are gradually added to the solution. The temperature is then slowly raised to 50 C. A yellow solution is formed from which grey crystals precipitate. After about 6 hours the solution is cooled, the hydrate of phenyl-aminm' imino-isoindolenine obtained in almost quantitative yield issucked off, washedwith some formamide and acetoneand dried. I u

r Example 18 12.2 parts 'of'sodiurrl amide are introduced into 150 parts of formamide at 0 C. with cooling and stirring.- 30 parts of 4.S-dichlorophthalonitrile are added in por-' tions to the clear solution. After gradually raising the temperature to 40 C. and stirring at this tempera-' ture for '12 hours the mixture is cooled and sucked off, the precipitate obtained is washed with acetone and ether anddried. The yield amounts to 27 parts of 4.5 -dichloro-1amino-3-imino-isoindolenine decompos= ing at about 265 C. while splitting oil" ammonia.

Example 19 60 parts of formamide, 3.5 parts of sodium amide and .107 parts of 3.4-dicyanodiphenylsulfone are reacted as described in Example 18. 9 parts of 1-amino-3-iminoisoindoleninyl-S- or -6-phenylsu1fone decomposing at abut 2l5 C. while splitting olr ammonia are thus obtained.

Example 20 32 .parts of pulverized sodium amide are introduced in portions into 320 parts of formamide at 0 C. with stirring and cooling with a freezing mixture of ice and common salt. 53 parts of A-4.5-4 methyl-tetrahydrophthalonitrile are added in portions to the clear solution. The temperature is allowed to raise to room tem-v perature, whereby colorless .crystals more and more precipitate from the initially yellow and then violet red colored solution. After about 12 hours tetrahydrated amino-imino-methyl-isoindolenine formed is sucked off and washed with acetone and ether. The product decomposes at about 130 C. while splitting off ammonia. The new substance is converted into the corresponding tetramethyloctahydrometal-phthalocyanine by means of metal salts, for instance, salts of copper, nickel and cobalt, in the presence of glycol or formamide, already at temperatures of about C. The new phthalocyanine dissolves in concentrated sulfuric acid with blue coloration. On gently heating the blue solution changes to brown, tetramethyyl-copper-phthalocyanine being formed with further dehydrogenation.

If, however, the tetrahydrogenated amino-imino-met hyl-isoindolenine is heated in nitrobenzene in the presence of a copper salt for a longer time tetramethyl-copper phthalocyanine is immediately obtained.

Example 21 40 parts of sodium amide are dissolved at 0 C. in 300 parts of formamide with stirring. 60 parts of 3.3'.4.4'-tetracyanodiphenyl are added in portions to the clear solution and gradually heated to 40-60 'C., a yellow brown solution being formed thereby. After about one hours stirring the solution is cooled with ice. Di(amino-imino-isoindoleninyl) precipitates in nearly quantitative yield in yellow, fine, small needles, which are sucked off, washed with some formamide and acetone and dried. D1(ammo-immo-isodindoleninyl) decomposes on heating without melting.

Example23 64 parts of phthalonit'rile are dissolved at 1'10f "C5 in 2000 parts of anhydrous benzene'and 23"parts of abso lute alcohol are added. Thereupon dry hydrogen 'chlo-- 200 partsof aboutr80% .nitricacid' are-obtained. On 1 pouring the solution-onto. small pieces of-ice the nitrate, of 1-amino-3-imino-isoindolenine is precipitated, sucked off, washed with water anddried in air.

Replacing phthalonitrile .by. the equivalent quantity of 3.4-dicyanodiphenyl the nitrate :of .1-amino-3-imino 5v(or, 1

-6-) phenylisoindolenine..is obtained."

Example 24 1' hydroxide solution and sodium hydrosulfite. 64.4 parts.

offormic acid are allowed'to'run into the solution which is, still stirred for some time; the. crystalline precipitate i formed is sucked 'off; washed with benzene and :driedin vacuo. About 167.7 parts of formate corresponding to 94.5 parts of 1-amino-3 imino-isoindolenine or 85.6% of the theoretical are thus obtained.

By replacing formic acid by equivalent amounts of other carboxylic acids corresponding saltsof the acids are obtained.

Example 25 35.6 parts .of 1.2-dicyanonaphthalene=are introduced in-.' to a.solution of'l.-15' parts of sodiumin-40.4-parts-of methyl alcohol diluted with 182.5 parts-of :benzene and stirred until the 1 .Z-dicyanonaphthalenehasbeen dissolved withsyellowscoloration.-- Thereupon 204 parts of-am-' moniat 100%) dissolved in methanol areadded and stirred until a test portiongives n0=bluc leuco compound inmcthyl-alcoholic, aqueoussolution- The precipitate obtained in a good yield (amounting to of the theoretical) is sucked offand .washed with benzene and ligroin-and driedjm vacuo. The .crude .product is obtained by.,concentratingits. methyl-alcoholic solutionin small, coarse. crystals melting at.204208 C. withgreen coloration.

Analysis. Calculated. C=73.9%I, H=4.61%, N: 21.52%; found. C=73.78%, H==4.35%, N=21.21%, O=0.77%

The l-amin03-imin0:4.S-benzodsoindolenine-'is difii. cultly soluble incold.methanohdissolves in methylalcoholic sodium hydroxide. solution with weakly yellowcoloration, however, precipitates again on adding=water because of the sodium saltbeing hydrolized. The product is dilficultly soluble. in acetone and comparatively difiicultly soluble in cold pyridine. It" dissolves in dilute, acetic acidwith yellow colorationandprecipitatesas.difficultly soluble nitrate in yellow needles by adding ammoniurn'.ni-v

tratc. It is solublein. dilutehydrochloric acid with yellowcoloration but precipitates again immediately as yellow hydrochloride which is, converted .into colorless. needles on boiling.

Example 26' 110 parts of 3'.4dicyano-(C)-phenyl-6-methyl benz-.

1.6 thiazol are introduced into.a=solution of 0.23 part of sodium in 55.4 parts of methanol diluted with 45.6 parts ofbenzene and stirred'until the starting product'hasjalmost'completely been dissolved. Thereupon'4.1 parts of ammonia (100%) dissolved in methanol are addedfandi the solution is kept at 35'40 C. until a test portion gives no longer a blue leuco compound. The crystalline precipitate 'issucked oif," washed with benzene and ligroin and". dried invacuo;

Amino-imino-isoindoleninyl-methylbenzthiazol is ob-- tained in a yield of about of the theoretical as green ish =g1fay powder containing already small quantities of phthaloc yanine and slightly dissolving in methanol -and acetone." The product is soluble-in-dilute aceticacidwitlr weakly yellowcoloration and precipitates as slightlysolublejweakly"yellow'nitrate when adding ammonium'nitrate solution. The-melting point of the product containing about molecule of methanol is at about 262-264'- C-'.

Example 27 18.96 parts of 4-methoxyphtha1onitrile are introduced at 20 C. into a solution of .0.69 part of sodium in 12.1 parts of methanol diluted in 67.5 parts of benzene and stirred until the starting product has been dissolved with yellow coloration. Thereupon 12.24 parts of ammonia dissolved in methanol are added and stirring is continued until a test portion gives no stable blue leuco compound in dilute sodium hydroxide solution and sodium hydrosulfit'e: The solution'is then concentrated-to a small vol umc-in 'vacuoythe crystals precipitating after some time are sucked off, washed with benzene and ligroin and dried in vacuo. 5-(or 6-)methoxy-1-amino-3-imino-isoindolenine; is obtained .in; good. yieldv int rod-shaped colorless crystalsvbecominggreen at C. anddecornposingatm 202 C. The 5- or .6 -)methoxy-1-amino-3-imino-isoindo+. lenine is soluble in water, soluble in methanol, diflicnltlysolubleinlacetone and gives a slightly soluble nitrate. portions of the (product. remaining in the benzene mother; liquor; may;be precipitated byaddlng ammonium bicar: bonate.

Themelting .pointz of the carbonate extracted -.from .the crude salt mixture with methanol and precipitatedwith, acetone is 25826l C.

On replacing ammonia by dimethylamine 5-(or 6-)- methoxy-l-dimethylamino-3-imino-isoindolenine is obtained in good yields.

By replacing 4-:methoXy-phthalonitrile by the equivalent amount of 4-ethoxy phthalonitrile. 5T(or 6-)ethoxy-1- amino-3-imino-isoindolenine is obtained after removing a difiicultly soluble. by-product melting at 217-218" C. and after concentrating the benzene solution. The latter product has a melting point of '182185- C. and exhibits similar properties as the above-said methoxy-compound.

Example.28

2.3. parts of; sodium are dissolved in ethanolandfthe solution is concentrated to 1823 parts, stirred withf52 64 partspffiliq'uid ammonia atabout 30 'C. and"l2.f8" parts of finely ground .phthalonitrile are rapidly stirredin: The starting product is' almost completely dissolvedwhile extracting ammonia by vigorously boiling'and l-ethoxy-3- imirio-isoindolenine'is then precipitated. The 'reactioh product;is, isolated-"after 10 minutes by diluting the reaction'mixture'with 100 parts of ice+water, suckin'g off," washing-with wate1' anddrying in vacuo at 30-40'C., ill" a yieldof92%' of the theoretical. 16 parts of diethoxy imino-dihydro-isoindolenine thus obtained are heated-with 36.4 parts of. concentrated aqueous ammonia on the waterbath. The product isdissolved within 3 minutes at 60- 65-'C; Traces ofnomdissolvedportionsare removed by filtering and the solution is chilled. A-thiclc'pasteof colorless,'almost'rectangulansmall crystals, which arewisiblby means 'of"a'microscope, is formed. The 'product'is" sucked oliiwashedwithsome water and dried. T he yield amountsv to 9 parts of amino-imino-isoindolenine. By"

adding parts of ammonium nitrate to the aqueous filtrate and to the wash water further 4.7 parts of the slightly soluble nitrate precipitate.

On replacing ammonia by methylamine, dimethylamine, other monoand dialkylamines or piperidine and morpholine the reaction yields a series of well-defined products wherein not only the alkoxybult also the imino-group is partly exchanged against alkylamino or alkylimino radi cals.

In the above reaction phthalonitrile may be replaced by 3.4-dicyano-diphenyl or 4-methoxyphthalonitrile. In this case the reaction yields the corresponding nuclear substituted 1-amino-3-imino-isoindolenine derivatives.

Example 29 11 parts of diethoxy-imino-dihydro-isoindolenine are heated with 36 parts of aniline on the water bath as described in Example 28. The starting product dissolves Within minutes at about 80 C. with deep yellow coloration'and presently light yellow small crystals precipitate. After stirring at 95 C. for another minutes the solution is cooled down to C., sucked off washed with methanol and dried. About 7 parts of 1-anilino-3-iminoisoindolenine forming greenish yellow, coarse small crystals melting at about 190-207 C. with decomposition and orange coloration are obtained. On acidifying the filtrate obtained as described above with dilute hydrochloric acid a slightly soluble, full, yellow colored hydrochloride precipitates. According to analysis the product obtained is a monohydrochloride of 1-phenylamino-3-phenyliminoisoindolenine.

Example 7.1 parts of 4-methylphthalonitrile are introduced at 20 C. with stirring into a solution of 0.29 part of sodium in 5.05 parts of methanol diluted with 28.1 parts of benzene and Stirring is continued at 20 C. until the intensity of the yellow solution is not further increased. Thereupon 1.28 parts of ammonia (100%) dissolved in methanol are added and stirring is continued until a test portion gives no longer a blue leuco compound with dilute sodium hydroxide solution and sodium hydrosuliite. The crystallized 5-(or 6-)methyl-1-amino-3-imino-isoindolenine is sucked oil and washed with benzene and ligroin. The product yields colorless, full, long prisms becoming green blue at 170 C., sintering at 181-182" C. and decomposing at l89190 C. with blue coloration.

The portions of the base remaining dissolved in the original reaction liquid may be precipitated with formic acid as formate which may be purified by dissolving in Water and precipitating with acetone.

Example 37 80.7 parts of a methanol solution containing about 8.0 parts of anhydrous sodium sulfide are mixed with 12.8 parts of finely distributed phthalonitrile at 20 C. The temperature rises within 15 minutes to -40 C. while the dinitrile dissolves with deep yelloW-temporarily deep green-yellow-coloration. The solution is stirred for another quarter of an hour and 20.0 parts of glacial acetic acid are gradually added drop by drop, the addition product formed thereby precipitating in crystalline form with brownish coloration. The product is sucked off and washed with methanol. The yield amounts to 13.4 parts of a product which takes on heating a very dark color and sinters at 220225 C. with decomposition. One part of a somewhat less pure product still precipitates from the mother solution by adding water. According to its chemical behavoir, mode of origin and elementary analysis the product formed is the mercapto-imino-isoindolenine or in the tautomeric form imino-thio-phthalimide. With aqueous sodium hydroxide solution an orange .colored sodium salt is obtained being difiicultly.

soluble when cold and dissolving on heating with orange coloration. The product dissolves in pyridine with red coloration and can be crystallized from this solvent. The

pyridine salt first precipitating thereby decomposes oil 7 is obtained which temporarily dissolves on heating, however, after some time deposits in reddish grey needles, presumably consisting of thiophthalimide and phthalimide.

With methanolic sodium hydrosulfide solution-prepared by cold saturation of a solution of anhydrous NazS in methanol with H28 and filtering off the precipitated sulfurthe mercapto-imino-isoindolenine described herein is obtained on heating within a short time. In this case the product deposts directly on cooling as orange colored sodium salt.

On boiling the mercapto-imino-isoindolenine in nitrobenzene for a short time blue needles with a metallic lustre of metal free phthalocyanine precipitate, hydrogen sulfide escaping thereby.

16.2 parts of mercapto-imino-isoindolenine in 147 parts of pyridine are mixed with 12 parts of ammonium nitrate with stirring. By gently heating on the water bath the starting product dissolves Within 10 mintues, an almost colorless compound precipitating from the red brown solution in a crystalline form. After stirring for half an hour at C. the solution is sucked off, the precipitate is washed with pyridine until clear, Washed again with water and dried. The almost colorless residue crystallizes from dilute aqueous ammonia in colorless needles and displays all properties of the amino-iminoisoindolenine-nitrate.

Example 32 1000 parts of acetamide and 128 parts of phthalonitrile are introduced .into a solution of 150 parts of potassium hydroxide in 400 parts of technical methanol. The solution thus obtained is heated for some time at 70 C. and is stirred still hot into a mixture of 1000 parts of ammonium nitrate and ice. The precipitating amino-iminoisoindolenine-nitrate is sucked oif, washed with water and dried. By boiling out with benzene and acetone the reaction product is obtained in good purity.

Example 33 145 parts of amino-imino-isoindolenine are stirred with 500 parts of aniline at 5060 C., the base slowly dissolving and anilino-imino-isoindolenine or its tautomeric forms crystallizing thereby while gaseous ammonia escapes. After 5 hours the solution is cooled with ice, sucked off, the precipitate is washed with methanol or avetone and dried. The light yellow product meltingv at 208 C. is obtained in analytically pure form. The yield amounts to of the theoretical.

On carrying out the reaction in boiling methanol the quantity of aniline may be reduced to about parts.

Example 34 parts of amino-imino-isoindolenine and 200 parts of aniline are heated with stirring.

The monosubstitution product temporarily crystallizing and redissolving on further heating is initially formed with splitting ofi of ammonia. The temperature is then raised to 200 C. and the solution is kept at this temperature until the splitting off of ammonia is practically complete. The initially clear melt has now become deep yellow. 1-

. phenylamino-3-phenylimino-isoindolenine crystallizes on cooling. Isolation is achieved by diluting the melt chilled to about 50 C. with benzene or acetone to double the volume, cooling with ice and further diluting with benzine.

The pure base is colorless, dissolves in alcohols, acetone and benzene and melts at 130 C. with yellow coloration and may be distilled at -168 C. under 5 mm. pressure without decomposition. The salts of the base are deep yellow colored. The product is obtained in a quantitative yield.

The addition product of 1 mol of aniline to 1 mol of plienylamino 3 phenylimino isoindolenine temporarily Hearst.

l9 crystallizes under the said conditions. This product melts at 7879 C. and splits off again the added aniline at 90-400 C.

Example 35 20 parts of amino-imino-isoindolenine and 30 parts of o-anisidine are heated with stirring as fast as possible in view of the active splitting off of ammonia and the solution is kept at 150 C. for minutes, the base charged being initially dissolved in anisidinc. Presently the reaction product crystallizes alrcady at the reaction temperature. The reaction mixture is then cooled, stirred with methanol, sucked off when ice-cold, the precipitate is washed with methanol and dried. o-Methoxy-anilinoimino-isoindolenine or its tautomers respectively are obtained in analytically pure form. The light yellow product melts at l95-200 C.

Example 36 parts of amino-imino-isoindolenine and parts of m-anisidine are heated with stirring at 150 C. until after 30 to minutes splitting off of ammonia is practically complete.

The cold, deep yellow melt is diluted with methanol and the deep yellow chloride of m-methoxyanilino-mmethoxy-phenylimino-isoindolenine is precipitated by means of hydrochloric acid.

Example 37 5 parts of amino-imino-isoindolenine are gently heated with excess cyclohexoxypropylamine with stirring. At 70-80 C. ammonia readily escapes. Thereupon the mixture is dissolved in water and weakly acidified with nitric acid. Crystallization of cyclohexoxypropylamino cyclohexoxy propylimino isoindoleninenitrate is completed by adding a solution of ammonium nitrate. 0n heating in glycol with copper acetate the product gives an easily soluble, brightly orange colored copper complex.

Example 38 20 parts of technical amino-imino-isoindolenine-nitrate are suspended in 100 parts of methanol at room temperature and 24 parts of monoethanolamine are rapidly added, the starting product being immediately dissolved thereby. Impurities in the solution are sucked oil as fast as possible and the filtrate is stirred for some time. Hydroxyethylamino-hydroxyethylimino-isoindolenine obtained in a quantitative yield is colorless and melts at 196 C.

In form of the free base the product is insoluble in most customary solvents when cold.

The reaction may also be accomplished in aqueous solution.

Example 39 20 parts of amino-imino-isoindolenine are reacted with 40 parts of p-nitraniline in boiling glacial acetic acid.

After the starting product has initially been dissolved 1.4 nitrophenylamino 3.4" nitrophenyl imino isoindolenine precipitates in light yellow small needles melting at 3113l2 C.

The product yields a sodium salt crystallizing from aqueous methanol in long, deep red needles which is hydrolized again with much water.

Example 40 and a half times the quantity of methanol weakly orange cold, washed with benzine and dried.

colored needles precipitate. After cooling the precipitate is sucked off, washed with methanol and dried. The yield amounts to 6.5 parts. On boiling for a longer time the yield of the orange red product is reduced. The product is readily soluble in hot benzene and crystallizes by adding methanol in felted, brownish red needles melting at 187 C. According to analysis (C=79.15, H: 4.6, N=l5.75%) the reaction product is a condensation product consisting of 2 mols of l-anilino-3-imino-isoindolenine having split oil one mol of NH: or of 3 mols of aminophenyl-imino-phthalimide having split oil 2 mols of NH3.

The orange red colored product melting at 187 C. is slightly soluble in methanol, however, immediately dissolves with deep orange yellow coloration by adding sodium hydroxide solution. By adding some water and hydrosulfite to the mixture an initially green, thereafter blue, vat-like solution is obtained which is decolorized on heating.

Example 41 24 parts of l-hydroxyethyl-amino 3 hydroxyethylimino-isoindolenine (prepared according to Example 59) are stirred with 100 parts of acetic anhydride, the temperature being allowed to raise to 50 C. After one hour the excess anhydride is decomposed by adding ice; common salt solution is added to the clear solution in equal volume and the precipitated 1-acetoxethyl-amino-3- acetoxethyl-imino-isoindolenine-hydrochloride is isolated by conventional methods. The reaction product is obtained as colorless, readily soluble salt.

Example 42 13 parts of amino-imino-isoindolenine and 30 parts of anesthesin are dissolved in 200 parts of anhydrous ethanol and the temperature is raised to 130 C. while distilling the alcohol. The reaction is completed within a short time. After stirring with cold alcohol, sucking off and drying 19 parts of analytically pure, light-yellow l-(pcarbothoxy-phenyl)-amino-3-imino-isoindolenine melting at 198-200 C. are obtained.

Example 43 The following substances are successively reacted in 100 parts of anhydrous ethanol at the said temperatures: 0.5 part of sodium at 2050 C., 26 parts of phthalonitrile at 4050 C., 40 parts of sulfanilic acid amide at C.

The mixture is gradually cooled with stirring and the crystallized 1(p-sulfonylamido-phenyl) amino-3-imino-isoindolenine is isolated in known manner. 50-51 parts of a light-yellow product melting at 212 C. are obtained.

Example 44 80 parts of phthalonitrile and 97 parts of 3-chloro aniline are reacted in a methylate solution consisting of 2 parts of sodium and 50 parts of methanol at temperatures between 30 and 45 C. Already after 30 minutes the reaction product begins to crystallize from the clear solution. After l020 hours isolution is accomplished in the usual manner. 115-120 parts of pure, light-yellow l-(3'-chlorophenyl)-amino-3-imino-isoindolenine melting at 214 C. are obtained.

Example 45 2 parts of sodium are dissolved in 150 parts of anhydrous methanol and in this solution 80 parts of phthalonitrile and 100 parts of 4-chloro aniline are caused to react. -110 parts of light-yellow 1-(4chlorophenyl)- amino-3-imino-isoindolenine melting at 206 C. are obtained.

Example 46 78 parts of l-(3'-chlorophenyl)-amino-3-imino-isoindolenine (prepared according to Example 44) and 33 parts of 3-chloro aniline are heated in 100 parts of xylene at C. for 7 hours, filtered at 100 C. and stirred when cold; the yellow crystallizate is sucked off when ice- 91 parts of l-(3'- 2i chlorophenyl) amino 3 (3"- chlorophenybimino-isoindolenine melting at 150 C. are obtained.

Example 47 78 parts of 1- (4-chlorophenyl)-amino-3-imino-isoindolenine (prepared according to Example 45), 39 parts of 4-chloro aniline and 100 parts of xylene are heated under reflux to the boil for -7 hours, all reactants being dissolved thereby, 96 parts of 1- (4'-chloropheny1)-amino- 3-(4-chlorophenyl)-imino-isoindolenine melting at 150 C. are obtained.

Example 48 2 parts of sodium, 80 parts of 4-anisidine, 80 parts of phthalonitrile are successively dissolved in 100 parts of anhydrous methanol, the temperature being allowed to raise up to 50-50 C. After 24 hours the crystallized product is sucked oil when ice-cold, washed and dried. 128 parts of 1-(4'-methoxy-phenyl)-amino-3-imino-isoindolenine melting at 190-195" C. are obtained.

Example 49 81 parts of 1-(4'-methoxyphenyl)-amino-3-imino-isoindolenine (prepared according to Example 48), 41 parts of 4-anisidine in 100 parts of xylene are heated to the boil for 68 hours and then cooled with stirring. 85-90 parts of l-(4-methoxyphenyl)-amino 3 (4" methoxyphenyl)-imino-isoindolenine are obtained. The yellow product melts at ISO-155 C.

Example 50 3 parts by weight of sodium are dissolved in 1000 parts by volume of methanol While stirring at room temperature. 160 parts of 2.3-dicyanopyrazine are introduced and a Weak stream of gaseous ammonia is passed through the solution at 20-30" C. The solution becomes reddish at the beginning, later on yellow and, after some hours, a grey crystalline precipitate consisting of 4.7-diaza-1- amino-3-imino-isodolenine forms to an increasing extent. After about 24 hours, the reaction product is filtered off, Washed with methanol and acetone and dried. The yield amounts to 160 parts by Weight.

Example 51 2 parts of sodium are dissolved in 700 parts by volume of methanol While stirring at room temperature. 70 parts of 3.4-dicyano-pyridine are introduced and a weak stream of gaseous ammonia is passed through the solution at 20-30" C. The solution becomes yellow at the beginning and, after about /2 hour, a grey crystalline precipitate consisting of 6-(or 5-)aza-1-amino 3-imino-isoindolenine forms to an increasing extent, which is suction filtered after about 24 hours, Washed with acetone and ether and dried. The yield amounts to 65 parts.

Example 52 19.2 parts of 4-ethoxy phthalic anhydride (M. P. 119-120") are introduced at 80 C. with stirring into a homogeneous melt of 32.4 parts of urea and 19.2 parts of ammonium nitrate with the addition of 0.03 part of ammonium molybdate. By heating the melt foams between 120 and 140 C., a brown-yellow, almost clear melt forms at l74176 C. After about 2 hours stirring a light crystalline precipitate forms almost instantaneously and the mixture becomes viscous. The mixture is diluted by quickly running in 100 parts of ice-cold water, stirred until a homogeneous paste has formed, filtered off, Washed with water and dried. 22.6 parts of almost colorless nitrate of 1-amino-3-irnino-5-(or 6-)-ethoxy-iso indolenine, which corresponds to 89 per cent of theoryare obtained. The product decomposes at about 247 C. It yields the free base with aqueous caustic soda solution. The base decomposes at about 175 C. with the formation of a green melt. a

In analogous manner the nitrate of 1-amino-3-irnino-5- (or 6-)methoxy-isoindolenine is obtained from .4- methoxy-phthalimide (M.P. of the pure product 216 C. un-

were" Example 53 is clear at the beginning becomes yellow-brown on heating and fine, orange-yellow colored crystals precipitate after heating for about 3 hours. The reaction mass becomes soon very viscous; therefore it is expedient to dilutes the mixture with 20 parts of nitrobenzene. After a reaction time of 3 hours the mixture is diluted with methanol after cooling to C. and suction filtered in the hot state. The reaction product is washed with methanol and water and thereafter dried. The nitrate obtained in good yield crystallizes in long lemon-yellow needles which melt at 236 C.

By reacting the nitrate with the calculated amount of caustic soda solution in a suspension of methanol and water 1-amino-3-imino-5- (or 6-) methylmercaptoisoindolenine melting at 207-208 C. is obtained. The crystallized, weakly yellowish base dissolves in dilute acetic acid with an intensive orange-yellow coloration.

Example 54 A moderate stream of ammonia is passed over a suspension of 53.5 parts of phthalonitrile in 64 parts of a solution of ammonia in methanol containing about 12.5 parts of ammonia and 0.65 part of 19.25 per cent of a solution of caustic soda in methanol. The suspension is gradually heated to 60 C. and stirred at this temperature for about 1 /2 hours. The phthalonitrile dissolves after about 1% hours, and l-amino-3-imino-isoindolenine (or its methanol addition compound) precipitates in coarse heavy crystals. A small sample of the reaction mixture in a mixture of pyridine and water gives a blue leuco compound with dilute caustic soda solution and sodium hyposulfite.

After about 1 /2 hours this leuco compound of a sample has disappeared almost completely; 0.20 part of glacial acetic acid is then added and stirring is continued at 60 C. for about /2 hour while passing over anmionia until no blue leuco compound is any longer visible.

When carrying out the reaction on a large scale pro duction it is not necessary to precipitate the 1-amino-3- imino-isoindolenine in pure form. In this case it is sufiicient to evaporate the reaction mixture to dryness in vacuo. About 62.1 parts of an almost colorless to faintly greenish product containing about 90.6 per cent of pure product, which corresponds to a yield of about 93 per cent of theory, are thus obtained.

Example 55 20.4 parts of 3.4-dicyano-diphenyl and 24.4 parts of a 10.5 per cent of solution of ammonia in methanol are introduced into the solution of 0.45 part of caustic soda in 48 parts of'methanol and the mixture is stirred at 40- 50 C. The dinitrile dissolves during 46 hours. The

solution is neutralized with 0.68 part of glacial acetic acid and concentrated to a small volume. The resulting 1-amino-3-imino-5-(or 6-)phenyl-isoindolenine can be isolated by stirring the concentrated methanol solution with about 80 parts of toluene and subsequently evaporating the solvent in vacuo. The product is obtained at loose powder in a yield of over per cent.

7 Example 56 250 parts of ground phthalonitrile are mixed while stirring with 500 parts by volume of liquid ammonia in i an autoclave at 140 C. under a pressure of -110 atm.

for 7 hours. After cooling the ammonia is blown oil and the light-grey, partially coarsely crystalline residue is mechanically removed and the mixture is heated to 95 C. About 285 parts (corresponding to about 98 per cent of theory) of almost pure l-amino-S-imino-isoindolenines are obtained. It is soluble in three times its quantity of water at 60 C. and crystallizes from its concentrated aqueous solution in long, colorless needles in form of a hydrate which can be dried at low temperature. The hydrate thus obtained can further be dried at 9095 C. without the danger of saponification, the anhydrobase being thus obtained. The pure anhydrobase melts at about 194-196 C. with green coloration and evolution of ammonia. By prolonged heating the aqueous solution having a strongly bitter taste the product is saponified to form mono-imino-phthalimide and, finally, phthalimide with the evolution of ammonia.

Upon addition of nitrate-, phosphate-, sulfiteor perchlorateions the corresponding colorless, very difficulty soluble salts precipitate in crystals in an almost quantitative yield.

The anhydrobase and its hydrate easily dissolve in methanol already in the cold but are very slightly soluble in either. acetone, benzene and cyclohexane, even in the heat. vents such as nitrobenzene and diehloro benzene and even in pyridine with green coloration and evolution of ammonia and partial formation of metal free phthalocyanine. By mixing the l-amino-3-irnino-isoindolenine with glycol while stirring a crystallized addition product, which is more fully described in Example 7, is obtained. By heating the addition product with metallic salts, particularly in the presence of solvents, under suitable, weakly reducing conditions the corresponding metal phthalocyanines are obtained with the splitting oil of ammonia, mostly in a very good yield and even at water bath temperatures. By shaking the aqueous solution of the base with benzoyl chloride in the presence of alkali a dibenzoyl compound forms, which is obtained from benzene in form of light yellow, bright, coarse crystals in pure form at 176l77 C.

Example 5 7 10 parts of 1-amino-3-imino-isoindolenine and 19 parts of N-amino-piperidinc-hydrochloride are dissolved in 150 parts of methanol and left standing at room temperature until the intensity of the yellow coloration no longer increases. By introducing 500 parts of Water with stirring, the reaction product precipitates in light yellow crystals. The yield amounts to 80 per cent of theory. The base, Cm H N5:l.-(l-piperidyl-amino)-3-(1"-piperidylimino)-isoindolenine is obtained analytically pure from pure starting materials. The base can be purified by recrystallizing from gasoline or another organic solvent, or by dissolving in an alcohol and precipitating with water. The base dissolves in dilute acids but not in pure water.

Example 58 parts of technical 2-amino-naphthalene-5-sulfonic acid and 10 parts of l-amino-3-imino-isoindolenine are dissolved in 160 parts of methanol. 50 parts of glacial acetic acid and the dark orange colored crystalline precipitate is suction filtered. The reaction product (34 parts) is apparently an internal salt of l-(2"-naphthyl- 5-sulfonic acid)-amino-3-imino-isoindolenine. It is only very sparingly soluble in Water and organic solvents.

The base quickly dissolves in higher boiling sol- No medium suitable for recrystallization has been found so far.

Example 59 In 25 parts of methanol are dissolved 4 parts of lamino-3-imino-isoindolenine and 9 parts of a parafiin amine of the statistical molecular weight 194 which is obtained from the so-called first runnings of fatty acids via the ketones obtainable therefrom according to conventional methods. By stirring the solution at 20 C. for two hours, the amino group of the isoindolenine derivative is exchanged for the paraffin amine. The reaction product which crystallizes is filtered off at 0 C., washed with some cold methanol and dried. 3.2 parts of parafiin-amino-imino-isoindolenine is obtained which, according to analysis, has the statistical summation formula C20.'1H32.2N3.

The base can be recrystallized from light gasoline.

Example 60 20 parts of 1-paraffin-amino-3-imino-isoindolenine, 20 parts of ethanolamine, and 20 parts of glacial acetic acid are successively dissolved in 160 parts of methanol and the solution is stirred at room temperature. After 30 minutes 1-hydroXyethyl-amino-3-hydroxyethyl-imino-isoindolenine begins to crystallize. Stirring is continued for another hour and the reaction product which is obtained in a quantitative yield is isolated by filtering, washing with water and drying.

Example 61 20 parts of l-anilino-3-ani]o-isoindolenine-hydrochloride are suspended in parts of methanol and 10 parts of ethanolamine are added. The solution which is dark yellow at the beginning gradually becomes lighter and 1hydroxyethyl-amino-3-hydroxyethyl-imino-isoindolenine soon begins to crystallize in almost quantitative yield. The product is isolated as described in the preceding example.

Example 62 18 parts of hexamethylene diamine and 20 parts of phthalonitrile are reacted in the sodium methylate solution prepared from 0.5 part of sodium and 80 parts of methanol at 4050 C. An amino-imino-isoindolenine derivative, (CsHsN3(CH2)6NH2), which is substituted with one amino-hexamethylene radical is formed. The reaction mixture is diluted with another parts of methanol as soon as the reaction, which is exothermic at the start, is complete.

The solution is further stirred at room temperature for a prolonged period, at least 24 hours. The product slowly crystallizes in a yield of 34- parts which, according to analysis, represents N .N -cyclohexamethylene-1- amino-3-imino-isoindolenine formed by intramolecular amine exchange reaction to which two molecules of methanol are attached.

N (C DE HN 2CH3OH F 2l0218 C.

Example 63 15 parts of l-amino-3-irnino-isoindolenine, and 40 parts of 4-amino-azo-benzene are heated in 200 parts of xylene until no ammonia is any longer split ofif. When cooling the dark oran e colored 1-benzene-azo-anilino-3-benzeneazo-anilo-isoindolenine crystallizes in good yield. The product is isolated by filtering and washing with cold methanol.

Example 64 13 parts of 1-amino-3-imino-isoindolenine and 20 parts of 2-amino-anthraquinone are rapidly heated with stirring in 100 parts of glycol and kept at ISO-160 C. for some time. The reactants dissolve and ammonia is split oif. After some minutes 24 parts of copper-red needles crystallize, which are isolated after cold stirring by filtering and washing with alcohol. The resulting 1-(2'-anthraquinonyl) -amino-3- (2"-anthraquinonyl) imino-isoindolenine shows a melting point of about 270 C.

Example 65 24 parts of 3.4-dicyano-diphenyl are reacted with 20 parts of 4-amino-diphenyl in a solution of 0.5 part of sodium in 160 parts of methanol.

1-(4'-phenyl)-anilino-3-imino-5-(or 6-)phenylisoindolenine obtained in a quantity of 27.5 parts is heated to the boil in 13 parts of 4-amino-diphenyl in 200 parts of xylene whereby 50 parts of xylene are slowly filtered off. When cooling and/or diluting with a mixture of petroleum and ether the dark-yellow colored 1'(4 phenyl)-anilino-3-(4"-phenyl)-anilo-5- (or 6-)phenylisoindolenine crystallizes. The product is isolated by filtering and washing with petroleum and ether.

Example 66 20 parts of 1-amino-3-imino-4-(or 7-)aza-isoindolenine nitrate are dissolved in 50 parts of 2-amino-ethanol and 80 parts of methanol, filtered, diluted with another 40 parts of methanol and stirred at room temperature for 2 to 3 hours. l-hydroxyl-ethyl-amino-3-hydroxyethylimino-4-(or 7-)aza-isoindolenine crystallizes in good yield. The product dissolves in alcohol, water and mixtures of acetone and water and is almost insoluble in dry acetone.

On replacing ethanolamine by aniline the corresponding phenyl-substituted isoindolenine derivative is obtained in good yields. By replacing ethanolamine by piperidine the reaction yields the 1-piperidine-3-imino-4-(or 7-)azaisoindolenine.

Example 67 8.8 parts of l-thiomethyl-3-imino-isoindolenine (weakly cream-colored needles which melt at 102-103 C. with evolution of gas and formation of a blue melt) are boiled with reflux with 8 parts of ammonium nitrate in 80 parts of methanol. Already after some minutes a greenish-grey slightly soluble product precipitates and methyl mercaptane escapes. The product (about parts) which is isolated after one hours heating under reflux, cooled to 40 C., suction filtered and washed with methanol, substantially represents the nitrate of l-amino-3-itninoisoindolenine. By dissolving the product in cold dilute caustic soda solution, filtering off the non-dissolved, colored contaminations and precipitating the clear, almost colorless filtrate with glacial aceticacid with the addition of some ammonium nitrate, the nitrate of 1- amino-3- imino-isoindolenine is obtained in colorless, sandy-crystalline form. (M. P.=2932-94 C.) By replacing ammonia by aniline or ethanolamine the correspondingly substituted 1-amino-3-imino-isoindolenine derivatives are obtained in good yields.

1-thiomethyl-3-imino-isoindolenine is obtained by finely grinding 16.2 parts of imino-thio-phthalimide (prepared according to Example 31) with 320 parts of water, heating the suspension formed to 60 C. and mixing with 25 parts by volume of caustic soda solution (40 per cent). The solution thus obtained is quickly filtered and quickly cooled to 20 C. by addition of ice. By stirring the resulting clear, brown-yellow solution with 15 parts of ,dimethyl sulfate at room'ternperature weakly yellowish colored crystals precipitate after a short time. The precipitate is filtered cit, washed with cold water and dried in the exsiccator. The yield amounts to 12 parts. The crude 1-thio-methyl-3-imino-isoindolenine is unstable on exposure to higher temperatures and light. It melts at about 90 C. with evolution of gas and formation of a dark green-blue colored melt. By dissolving the melt in methanol at a max. temperature of 40 C. and slowly diluting with water the product is obtained in creamcolored needles of the melting point 102-103 C. after green coloration from C. By heating the thio-methyl ether in nitrobenzene and even in glacial acetic acid metalfree phthalocyanine is obtained.

Example 68 A weak current of ammonia is passed over a suspension of 0.28 part of methanolic caustic soda solution 19.25%) 19.8 parts of methanolic ammonia (corresponding to 3.75 parts of ammonia) and 7.19 parts of 4-ethoxyphthalonitrile (prepared by splitting off water from 4 ethoxy phthalamide, M. P. 133-134 C.) until the 4-ethoxy-phthalonitrile has dissolved and 4- ethoxy-phthalonitrile is no longer precipitated from a sample of the suspension on diluting with water and some drops of caustic soda solution. Thereupon 0.08 part of glacial acetic acid is added and ammonia is passed over the solution for another /2 hour. By evaporating the solution 5-(or 6-)ethoxy-1-amino-3-imino-isoindolenine is obtained as light crystalline powder which contains only small quantities of sodium acetate and can be employed immediately for further reaction. The crude product becomes greenish at 166-174 C. and decomposes at 176-177" C. with foaming. It is easily soluble in methanol and dilute acetic acid and difiicultly in acetone. The yellow solution in hydrochloric acid is quickly decolorized by hydrolysis of S-(or 6-)ethoxy-l-amino-3- imino-isoindolenine. The slightly soluble nitrate of the base can be precipitated by mixing the methanolic aqueous solution with ammonium nitrate solution and weakly acidifying with acetic acid. The nitrate which can advantageously be utilized for producing the pure base is weakly lemon-yellow colored. It becomes darker at 240 C. and decomposes at 244-245 C. with foaming.

By decomposing the nitrate suspended in methyl alcohol with the calculated amount of caustic soda solution and diluting the resulting solution with water, the pure Example 69 When replacing'in the preceding example 4-ethoxyphthalonitrile by the equivalent amount of 4-phenoxyphthalonitrile (prepared by splitting off water from 4- phenoxy phthalamide, M. P. 101-102 C.)' a solution of 5- (or 6-)phenoxy-l-arnino-3-imino-isoindolenine is obtained. By evaporating the solution the base remains behind as a brittle, yellow colored mass which can easily be pulverized. The mass is easily soluble in methanol, difficultly soluble in acetone and shows properties similar to the ethoxy compound described in the preceding example. The slightly soluble nitrate of the base, which is strongly lemon-yellow colored, becomes dark at temperatures above 250 C. and decomposes at 264--265 C. with foaming. The base prepared from the nitrate melts at 94-96 C. to form a dark green liquid which decomposes at 101-102 C. with foaming.

The syntheses described in the foregoing paragraphs B; C'and D are equivalent to each other, i. e. it is possible to produce any 1-amino-3-imino-isoindolenine derivative directly from dinitrile by addition of an amine as well as by exchange of the alkoxyor amino group isoindolenine derivatives for the same amine. In the foregoing examples the processes according to paragraphs B, C and D are interchangeable as will be apparent to anyone skilled in the art. Therefore it is unnecessary to specifically describe each of these processes for each and every isoindolenine derivative hereinbefore described, the disclosure of one process constituting also a full disclosure of the other possible methods. Furthermore each 1-amino-3-imino-isoindolenine derivative obtainable by the method of production according to paragraph A may also be obtained by the processes described in paragraphs B, C and D.

We claim:

1. The process for the production 1-arnino-3-iminoisoindolenine derivatives which comprises reacting at temperatures up to about 160 C. an 1-amino-3-iminoisoindolenine of the general formula N NE wherein R stands for a radical selected from the group consisting of hydrogen, alkyl, aryl having no more than three rings, cycloalkyl and aralkyl and X for the atoms necessary to complete an aromatic ring selected from the group consisting of the benzene ring, pyridine ring, pyrazine ring and naphthalene ring, with an amine of the formula wherein R1 and R2 stand for radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl and aryl having no more than three rings, and R1-|R2 stand for a radical selected from the group consisting of the divalent radicals -(CHz)5- and both free valences being attached to the nitrogen atom.

2. A process as claimed in claim 1 in which the reaction is carried out in an inert solvent.

3. As new compounds 1-arnino-3-imino-isoindolenine derivatives of the general formula wherein Z stands for the atoms necessary to complete an aromatic ring selected from the group consisting of a pyridine ring, a pyrazine ring and a naphthalene ring, and R1, R2 and R stand for radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralltyl and aryl having no more than three rings, and R1+R2 stand for a radical selected from the group consisting of the divalent radicals (CH2)5- and wherein n is an integer from 0 to 7, both inclusive.

5. A compound of the formula:

wherein n is an integer from 0 to 7, both inclusive.

6. A compound of the formula:

wherein n is an integer from 0 to 7, both inclusive.

7. A compound of the formula:

wherein n is an integer from 0 to 7, both inclusive.

8. A compound of the formula:

30 10. A compound of the formula: 11. A compound of the formula NH, NH: 5 N "E 5 \N 0 0 OC=NH 7 1 m N c w c cfi 1E1:

o No references cited. 

1. THE PROCESS FOR THE PRODUCTION 1-AMINO-3-IMINOISOINDOLENINE DERIVATIVES WHICH COMPRISES REACTING AT TEMPERATURES UP TO ABOUT 160*C. AN 1-AMINO-2-IMINOISOINDOLENINE OF THE GENERAL FORMULA 